Azeotropic distillation

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Phase diagram (left) and process flow diagram (right) of an apparatus for the azeotropic distillation with "material separation agent". In this case the phase diagram includes a zone where components are not miscible, so following the condensation of the azeotrope, it is possible to separate the liquid components through decantation. Azeotr distill.svg
Phase diagram (left) and process flow diagram (right) of an apparatus for the azeotropic distillation with "material separation agent". In this case the phase diagram includes a zone where components are not miscible, so following the condensation of the azeotrope, it is possible to separate the liquid components through decantation.

In chemistry, azeotropic distillation [1] is any of a range of techniques used to break an azeotrope in distillation. In chemical engineering, azeotropic distillation usually refers to the specific technique of adding another component to generate a new, lower-boiling azeotrope that is heterogeneous (e.g. producing two, immiscible liquid phases), such as the example below with the addition of benzene to water and ethanol.

Contents

Common Equipment used in Azeotropic Distillation Common equipment used in Azeotropic Distillation.jpg
Common Equipment used in Azeotropic Distillation

This practice of adding an entrainer which forms a separate phase is a specific sub-set of (industrial) azeotropic distillation methods, or combination thereof. In some senses, adding an entrainer is similar to extractive distillation.

Material separation agent

The addition of a material separation agent, such as benzene to an ethanol/water mixture, changes the molecular interactions and eliminates the azeotrope. Added in the liquid phase, the new component can alter the activity coefficient of various compounds in different ways thus altering a mixture's relative volatility. Greater deviations from Raoult's law make it easier to achieve significant changes in relative volatility with the addition of another component. In azeotropic distillation the volatility of the added component is the same as the mixture, and a new azeotrope is formed with one or more of the components based on differences in polarity. [2] If the material separation agent is selected to form azeotropes with more than one component in the feed then it is referred to as an entrainer. The added entrainer should be recovered by distillation, decantation, or another separation method and returned near the top of the original column. [3]

Distillation of ethanol/water

A common historical example of azeotropic distillation is its use in dehydrating ethanol and water mixtures. For this, a near azeotropic mixture is sent to the final column where azeotropic distillation takes place. Several entrainers can be used for this specific process: benzene, pentane, cyclohexane, hexane, heptane, isooctane, acetone, and diethyl ether are all options as the mixture. [2] Of these benzene and cyclohexane have been used the most extensively, but since the identification of benzene as a carcinogen, toluene is used instead.[ citation needed ]

A Dean-Stark apparatus is used in azeotropic drying or dehydration processes: 1 stirrer bar/anti-bumping granules, 2 still pot, 3 fractionating column, 4 thermometer/boiling point temperature, 5 condenser, 6 cooling water in, 7 cooling water out, 8 burette, 9 tap, 10 collection vessel Dean-Stark apparatus.svg
A Dean–Stark apparatus is used in azeotropic drying or dehydration processes: 1 stirrer bar/anti-bumping granules, 2 still pot, 3 fractionating column, 4 thermometer/boiling point temperature, 5 condenser, 6 cooling water in, 7 cooling water out, 8 burette, 9 tap, 10 collection vessel

Pressure-swing distillation

Another method, pressure-swing distillation, relies on the fact that an azeotrope is pressure dependent. An azeotrope is not a range of concentrations that cannot be distilled, but the point at which the activity coefficients of the distillates are crossing one another. If the azeotrope can be "jumped over", distillation can continue, although because the activity coefficients have crossed, the component which is boiling will change. For instance, in a distillation of ethanol and water, water will boil out of the remaining ethanol, rather than the ethanol out of the water as at lower concentrations.

Overall the pressure-swing distillation is a very robust and not so highly sophisticated method compared to multi component distillation or membrane processes, but the energy demand is in general higher. Also the investment cost of the distillation columns is higher, due to the pressure inside the vessels.

Molecular sieves

For low boiling azeotropes distillation may not allow the components to be fully separated, and must make use of separation methods that does not rely on distillation. A common approach involves the use of molecular sieves. Treatment of 96% ethanol with molecular sieves gives anhydrous alcohol, the sieves having adsorbed water from the mixture. The sieves can be subsequently regenerated by dehydration using a vacuum oven.

Dehydration reactions

In organic chemistry, some dehydration reactions are subject to unfavorable but fast equilibria. One example is the formation of dioxolanes from aldehydes: [4]

RCHO + (CH2OH)2 RCH(OCH2)2 + H2O

Such unfavorable reactions proceed when water is removed by azeotropic distillation.

See also

Related Research Articles

<span class="mw-page-title-main">Distillation</span> Method of separating mixtures

Distillation, also classical distillation, is the process of separating the component substances of a liquid mixture of two or more chemically discrete substances; the separation process is realized by way of the selective boiling of the mixture and the condensation of the vapors in a still.

<span class="mw-page-title-main">Ethanol</span> Organic compound (CH₃CH₂OH)

Ethanol is an organic compound with the chemical formula CH3CH2OH. It is an alcohol, with its formula also written as C2H5OH, C2H6O or EtOH, where Et stands for ethyl. Ethanol is a volatile, flammable, colorless liquid with a characteristic wine-like odor and pungent taste. It is a psychoactive recreational drug, and the active ingredient in alcoholic drinks.

<span class="mw-page-title-main">Azeotrope</span> Mixture of two or more liquids whose proportions do not change when the mixture is distilled

An azeotrope or a constant heating point mixture is a mixture of two or more components in fluidic states whose proportions cannot be altered or changed by simple distillation. This happens because when an azeotrope is boiled, the vapour has the same proportions of constituents as the unboiled mixture. Azeotropic mixture behavior is important for fluid separation processes.

Fractional distillation is the separation of a mixture into its component parts, or fractions. Chemical compounds are separated by heating them to a temperature at which one or more fractions of the mixture will vaporize. It uses distillation to fractionate. Generally the component parts have boiling points that differ by less than 25 °C (45 °F) from each other under a pressure of one atmosphere. If the difference in boiling points is greater than 25 °C, a simple distillation is typically used.

Pervaporation is a processing method for the separation of mixtures of liquids by partial vaporization through a non-porous or porous membrane.

<span class="mw-page-title-main">Extractive distillation</span>

Extractive distillation is defined as distillation in the presence of a miscible, high-boiling, relatively non-volatile component, the solvent, that forms no azeotrope with the other components in the mixture. The method is used for mixtures having a low value of relative volatility, nearing unity. Such mixtures cannot be separated by simple distillation, because the volatility of the two components in the mixture is nearly the same, causing them to evaporate at nearly the same temperature at a similar rate, making normal distillation impractical.

<span class="mw-page-title-main">Steam distillation</span> Method of separation in organic chemistry

Steam distillation is a separation process that consists of distilling water together with other volatile and non-volatile components. The steam from the boiling water carries the vapor of the volatiles to a condenser; both are cooled and return to the liquid or solid state, while the non-volatile residues remain behind in the boiling container.

<span class="mw-page-title-main">Molecular sieve</span> Filter material with homogeneously sized pores in the nanometer range

A molecular sieve is a material with pores of uniform size. These pore diameters are similar in size to small molecules, and thus large molecules cannot enter or be adsorbed, while smaller molecules can. As a mixture of molecules migrates through the stationary bed of porous, semi-solid substance referred to as a sieve, the components of the highest molecular weight leave the bed first, followed by successively smaller molecules. Some molecular sieves are used in size-exclusion chromatography, a separation technique that sorts molecules based on their size. Another important use is as a desiccant. Most of molecular sieves are aluminosilicate zeolites with Si/Al molar ratio less than 2, but there are also examples of activated charcoal and silica gel.

Reactive distillation is a process where the chemical reactor is also the still. Separation of the product from the reaction mixture does not need a separate distillation step which saves energy and materials. This technique can be useful for equilibrium-limited reactions such as esterification and ester hydrolysis reactions. Conversion can be increased beyond what is expected by the equilibrium due to the continuous removal of reaction products from the reactive zone. This approach can also reduce capital and investment costs.

<span class="mw-page-title-main">Volatility (chemistry)</span> Tendency of a substance to vaporize

In chemistry, volatility is a material quality which describes how readily a substance vaporizes. At a given temperature and pressure, a substance with high volatility is more likely to exist as a vapour, while a substance with low volatility is more likely to be a liquid or solid. Volatility can also describe the tendency of a vapor to condense into a liquid or solid; less volatile substances will more readily condense from a vapor than highly volatile ones. Differences in volatility can be observed by comparing how fast substances within a group evaporate when exposed to the atmosphere. A highly volatile substance such as rubbing alcohol will quickly evaporate, while a substance with low volatility such as vegetable oil will remain condensed. In general, solids are much less volatile than liquids, but there are some exceptions. Solids that sublimate such as dry ice or iodine can vaporize at a similar rate as some liquids under standard conditions.

The Marcusson apparatus, Dean-Stark apparatus, Dean–Stark receiver, distilling trap, or Dean–Stark Head is a piece of laboratory glassware used in synthetic chemistry to collect water from a reactor. It is used in combination with a reflux condenser and a distillation flask for the separation of water from liquids. This may be a continuous removal of the water that is produced during a chemical reaction performed at reflux temperature, such as in esterification reactions. The original setup by Julius Marcusson was refined by the American chemists Ernest Woodward Dean (1888–1959) and David Dewey Stark (1893–1979) in 1920 for determination of the water content in petroleum.

A zeotropicmixture, or non-azeotropic mixture, is a mixture with liquid components that have different boiling points. For example, nitrogen, methane, ethane, propane, and isobutane constitute a zeotropic mixture. Individual substances within the mixture do not evaporate or condense at the same temperature as one substance. In other words, the mixture has a temperature glide, as the phase change occurs in a temperature range of about four to seven degrees Celsius, rather than at a constant temperature. On temperature-composition graphs, this temperature glide can be seen as the temperature difference between the bubble point and dew point. For zeotropic mixtures, the temperatures on the bubble (boiling) curve are between the individual component's boiling temperatures. When a zeotropic mixture is boiled or condensed, the composition of the liquid and the vapor changes according to the mixtures's temperature-composition diagram.

Batch distillation refers to the use of distillation in batches, meaning that a mixture is distilled to separate it into its component fractions before the distillation still is again charged with more mixture and the process is repeated. This is in contrast with continuous distillation where the feedstock is added and the distillate drawn off without interruption. Batch distillation has always been an important part of the production of seasonal, or low capacity and high-purity chemicals. It is a very frequent separation process in the pharmaceutical industry.

<span class="mw-page-title-main">Heteroazeotrope</span>

A heteroazeotrope is an azeotrope where the vapour phase coexists with two liquid phases. Sketch of a T-x/y equilibrium curve of a typical heteroazeotropic mixture

In thermodynamics and chemical engineering, the vapor–liquid equilibrium (VLE) describes the distribution of a chemical species between the vapor phase and a liquid phase.

This page contains tables of azeotrope data for various binary and ternary mixtures of solvents. The data include the composition of a mixture by weight, the boiling point (b.p.) of a component, the boiling point of a mixture, and the specific gravity of the mixture. Boiling points are reported at a pressure of 760 mm Hg unless otherwise stated. Where the mixture separates into layers, values are shown for upper (U) and lower (L) layers.

Relative volatility is a measure comparing the vapor pressures of the components in a liquid mixture of chemicals. This quantity is widely used in designing large industrial distillation processes. In effect, it indicates the ease or difficulty of using distillation to separate the more volatile components from the less volatile components in a mixture. By convention, relative volatility is usually denoted as .

Salt-effect distillation is a method of extractive distillation in which a salt is dissolved in the mixture of liquids to be distilled. The salt acts as a separating agent by raising the relative volatility of the mixture and by breaking any azeotropes that may otherwise form.

Isopropyl alcohol is a colorless, flammable organic compound with a pungent alcoholic odor.

<span class="mw-page-title-main">Residue curve</span>

A residue curve describes the change in the composition of the liquid phase of a chemical mixture during continuous evaporation at the condition of vapor–liquid equilibrium. Multiple residue curves for a single system are called residue curves map.

References

  1. Kister, Henry Z. (1992). Distillation Design (1st ed.). McGraw-Hill. ISBN   0-07-034909-6.
  2. 1 2 Kumar, Santosh; et al. (2010), "Anhydrous ethanol: A renewable source of energy.", Renewable and Sustainable Energy Reviews, doi:10.1016/j.rser.2010.03.015
  3. Treybal (1980). Mass-Transfer Operations (3rd ed.). McGraw-Hill.
  4. Wiberg, Kenneth B. (1960). Laboratory Technique in Organic Chemistry . McGraw-Hill series in advanced chemistry. New York: McGraw Hill. ASIN   B0007ENAMY.